JP2020001038A - Zeolite adsorbent having large outer surface area and use of zeolite adsorbent - Google Patents

Abstract

To provide a zeolite adsorbent which has good movement characteristics and is useful for separation and purification of a gas, and usage of the same.SOLUTION: Provided are a zeolite adsorbent containing at least one kind of FAU-type zeolite, and having an outer surface area exceeding 20 m.g, a non-zeolite phase (PNZ) content such as 0<PNZ≤30%, a Si/Al atomic ratio between 1 and 2.5, a meso pore volume between 0.08 cm.gand 0.25 cm.g, and a (Vmicro-Vmeso)/Vmicro ratio between -0.5 and 1.0 excluding a border value; and usage of the same.SELECTED DRAWING: None

Description

  The present invention is a zeolite adsorbent material in agglomerated form, comprising at least one faujasite-type zeolite, wherein the adsorbent has a large external surface area characterized by nitrogen adsorption, a large external surface area for gas phase separation. Pore volume, in particular, PSA (pressure swing adsorption: pressure swing adsorption) type, VSA (vacuum swing adsorption: vacuum swing adsorption) type, VPSA (combined type method of PSA and VSA mentioned above) type, or RPSA (rapid pressure) swing adsorption: high-speed pressure swing adsorption (TSA) -type pressure swing method, TSA (temperature swing adsorption: temperature swing-adsorption) type temperature swing method, and / or the like. PTSA is: has a large pore volume for the gas-phase separation in (pressure and temperature swing adsorption the pressure temperature swing adsorption) type pressure temperature swing method, the use of a zeolite adsorbent material.

  The present invention also relates to a method for gas separation and purification using said zeolite adsorbent having a large external surface area.

  The present invention also relates to a zeolite adsorbent material having a large external surface area and comprising lithium and / or calcium and / or sodium that can be used in connection with the present invention.

  The use of this type of agglomerate is particularly advantageous in applications where the speed of movement, adsorption capacity per unit volume and small pressure drop, which are parameters determining the overall efficiency and productivity of the process, are desired.

  Extensive efforts have been made over the last few years in the adsorption separation process to increase the hourly productivity of the adsorbent bed, especially by increasing the frequency of the adsorption / desorption cycle. This means that the adsorbent used becomes saturated by adsorption with respect to properties other than thermodynamic adsorption properties, and that the desorbed gas is released in a cycle that becomes shorter and shorter during desorption. Must be possible. Therefore, the adsorbent must be designed to allow the most efficient mass transfer, i.e. the gas to be separated or purified reaches the adsorption site as quickly as possible and, in addition, It must be designed to be desorbed as quickly as possible.

  Several paths have been explored to achieve the above objectives. The first method proposed by the literature is to reduce the size of the adsorbent particles. The effect of reducing the size of the adsorbent particles is to allow faster gas diffusion into the macroporous network, and the rate constant for mass transfer depends on the particle diameter (or adsorbent size). It is generally accepted that, in some forms, it is inversely proportional to the square of the equivalent dimension). See, for example, "Adsorbent particle size effects in the separation of air by rapid pressure swing advertisement", byE. See Alpay et al. , Chemical Engineering Science, 49 (18), 3059-3075, (1994).

  Document WO 2008/152319 describes the preparation of small, mechanically strong sorbents by spray drying, for example those used in portable medical oxygen concentrators as indicated by document US 2013/0216627. Is described. The main disadvantage of reducing the size of the adsorbent particles is the increased pressure drop in the adsorbent and the large energy consumption associated with this increased pressure drop. These disadvantages are not particularly acceptable in the adsorption step of industrial gas production.

  The second method is to improve the ability of the adsorbent to move intragranularly without changing the size of the adsorbent. International applications WO99 / 43415, WO99 / 43416, WO99 / 43418, WO2002 / 049742 and WO2003 / 004135 have improved kinetic sorbents obtained by converting a cohesive binder into a zeolite-type active substance. A related gas separation method is described, which adsorbent is more efficient than conventional particles.

  Document WO 2008/051904 proposes a method for producing an adsorbent by extrusion / spheronization of zeolite beads based on LiX-type zeolites with improved diffusion. Part of the document WO 2008/109882 describes the preparation of a high crush strength adsorbent with improved mass transfer from a LiX-type zeolite or LiLSX-type zeolite and less than 15% of a silicon-containing binder introduced in colloidal form. Is described.

  Application EP 1240939 has a specific ratio between the kinetic transport constant of an adsorbable compound in the gas phase and the kinetic transport constant of an adsorbable compound in the solid phase for use in the PSA or VSA method. It is proposed to select an adsorbent. Document US Pat. No. 6,328,786 defines a minimum threshold value for mechanical strength and rate coefficient above which the adsorbent becomes preferred for use in the PSA process. Application EP 1048345 describes a high macroporous sorbent produced by the technique of spheronization and freeze-drying.

  A third method is to use a variety of molding techniques that combine both reduced active material thickness and a sufficiently wide channel cross-section to allow flow with limited pressure drop. The use of a simple geometry improves contact with the adsorbent. An adsorbent sheet and an adsorbent fabric, a honeycomb-type monolith structure or a foam, and the like are included.

  Document FR 2794993 proposes the use of non-homogeneous beads in which a thin peripheral layer of sorbent is coated on an inert core, thus reducing the diffusion distance without increasing the pressure drop. are doing. This system has the disadvantage that it has a low volumetric efficiency, ie a significant part of the adsorbent is taken up by substances which are inert with respect to the adsorption. This drawback has a significant effect on the size of the facility, and therefore also on the investment in the facility or the weight of the facility, which is portable purification / separation equipment, such as medical oxygen enrichment. In the case of the device, it can be a drawback.

  Patent applications US2012 / 0093715 and US2013 / 0052126 teach that monolithic zeolite structures having a hierarchical structure can be formed by adding polymers to the synthetic reaction medium. In the case of adsorbent sheets and adsorbent fabrics, the resulting solids have a very large macropore volume and a very large mesopore volume, and therefore these solids have a low adsorption capacity per unit volume. It is not very dense and has low volumetric efficiency.

International Publication No. 2008/152319 US Patent Application Publication No. 2013/0216627 WO 99/43415 WO 99/43416 International Publication No. WO 99/43418 International Publication No. 2002/049742 International Publication No. WO 2003/004135 International Publication No. 2008/051904 International Publication No. 2008/109882 European Patent No. 1240939 U.S. Pat. No. 6,328,786 European Patent No. 1048345 French Patent Invention No. 2794993 US Patent Application Publication No. 2012/0093715 US Patent Application Publication No. 2013/0052126

"Adsorbent particle size effects in the separation of air by rapid pressure swing adsorption", byE. See Alpay et al. , Chemical Engineering Science, 49 (18), 3059-3075, (1994).

  Therefore, all of these adsorbent geometries with different properties often have a reduced active substance content, thanks to inert binders or other mechanical reinforcing fibers, or the resulting material has It is not very dense, causing problems with relatively complex processing, mechanical fatigue or wear resistance and low volumetric efficiency.

  Accordingly, there remains a need for a zeolite adsorbent that has good transfer properties and that is useful for gas separation and purification without the disadvantages associated with the use of prior art adsorbents. In particular, there remains a need for zeolite adsorbents that have greater adsorption capacity and better adsorption / desorption rates, and that allow for more intensive use of methods, especially PSA, TSA or VPSA methods. I have.

  Here, we have found that the above objectives can be fully or at least partially achieved by adsorbents dedicated for use in gas separation and purification, as described below.

Thus, according to a first aspect, the present invention relates to the use of at least one zeolite adsorbent material comprising at least one FAU type zeolite for gas separation, wherein said adsorbent comprises:
- measured by nitrogen adsorption, expressed as ^{m 2} per adsorbent 1 g ^{20 m} 2. g ⁻¹ , preferably 20 m ² . 300m ² from g ^-1. g ⁻¹ , more preferably 30 m ² . 250m ² from g ^-1. g ⁻¹ , even more preferably 40 m ² . 200m ² from g ^-1. g- ¹ , most specifically 50 m ² . 200m ² from g ^-1. an external surface area between g- ¹ ;
0 <PNZ ≦ 30%, preferably 3% ≦ PNZ ≦ 25%, more preferably 3% ≦ PNZ ≦ 20%, advantageously 3% ≦ PNZ ≦ 25% by weight relative to the total weight of the adsorbent as measured by XRD (X-ray diffraction) A non-zeolitic phase (PNZ) content such that 5% ≦ PNZ ≦ 20%, even more preferably 7% ≦ PNZ ≦ 18%;
・ 0.08 cm ³ including the boundary value. 0.25cm ³ from g ^-1. g ⁻¹ , preferably 0.08 cm ³ . g ⁻¹ to 0.22 cm ³ . between g ^-1, more preferably 0.09 cm ^3. 0.20cm ³ from g ^-1. g ⁻¹ , more preferably 0.10 cm ³ . 0.20cm ³ from g ^-1. a mesopore volume (Vmeso) between g- ¹ ;
The Si / Al atoms of the adsorbent between 1 and 2.5, preferably between 1 and 2.0, more preferably between 1 and 1.8, and most preferably between 1 and 1.6 And wherein all measurements are performed on an adsorbent material that has been exchanged for at least 95% by sodium.

2 shows an image obtained by transmission electron microscopy (TEM) of the zeolite synthesized as described above. Fig. 4 illustrates a manufactured assembly. Figure 3 shows the oxygen content of the stream produced at the outlet (9) as a function of the desorption time defined for the materials of Examples 1 and 2;

  As used herein, the term "FAU-type zeolite" refers to faujasite-type zeolites, preferably mesoporous faujasites, selected from LSX-type zeolites, MSX-type zeolites, X-type zeolites and Y-type zeolites and mixtures thereof. Means type zeolite. According to one embodiment, the zeolite adsorbent material comprises FAU-type zeolites (LSX-type zeolites, MSX-type zeolites, X-type zeolites, Y-type zeolites), LTA-type zeolites, CHA-type zeolites (chabazite), HEU-type zeolites ( Selected from LSX-type zeolites, MSX-type zeolites and X-type zeolites, and mixtures of two or more of these. It may further comprise at least one other zeolite.

  Other zeolites may be present in small amounts in the sorbents of the invention or may be used in the method of the invention. These zeolites can be considered contaminants, especially because they do not contribute to gas adsorption, in other words, they are inert with respect to gas adsorption. By way of non-limiting example, these zeolites include sodalite, hydroxysodalite, P-type zeolites, and other zeolites that are inert with respect to gas adsorption.

  The various types of zeolites present in the zeolitic adsorbent material are measured by XRD. The amount of zeolite is also measured by XRD and is expressed as a percentage by weight relative to the total weight of the adsorbent material.

Thus, in the present invention, the term "non-zeolite phase" (or "PNZ") refers to any non-zeolite defined above, referred to as "zeolite phase" or "PZ", which is present in the adsorbent material. Represents the phase of The amount of non-zeolitic phase is such that the sum is 100%, in other words:
% PNZ = 100-% PZ
Where% PNZ represents the weight percent of PNZ relative to the total weight of the adsorbent, and% PZ represents the weight percentage of zeolite relative to the total weight of the adsorbent. Represents the weight percentage of the phase.

  The expression "adsorbent at least 95% exchanged by sodium" is intended to mean that at least 95% of the exchangeable cationic sites in the zeolite phase are occupied by sodium cations.

This zeolite sorbent material that has been exchanged by at least 95% by sodium can be obtained according to the following protocol, and is preferably obtained according to the following protocol. The zeolite adsorbent material to be exchanged by sodium is added to a sodium chloride solution with 1 mol of NaCl per liter and a liquid to solid ratio of 10 ml. It is introduced at 90 ° C. for 3 hours at g ⁻¹ . This operation is repeated n times, where n is at least equal to 1, preferably at least equal to 2, preferably at least equal to 3, more preferably at least equal to 4.

The solids obtained from the (n-1) th and n-th exchange operations were sequentially added to 20 ml. Wash four times by immersion in water in the ratio g ⁻¹ and then dry in air at 80 ° C. for 12 hours before analyzing by X-ray fluorescence. If the weight percentage of sodium oxide in the zeolite adsorbent material is stable at ± 1% between the (n-1) th exchange operation and the n-th exchange operation, the zeolite adsorbent material is "at least by sodium. 95% exchanged form ". If necessary, further exchanges are performed as described above until the weight percentage of sodium oxide stabilizes at ± 1%.

  In particular, continuous batch cation exchange is carried out with a large excess of sodium chloride until the weight percentage of sodium oxide of the above zeolite adsorbent material is stable at ± 1% as determined by X-ray fluorescence chemical analysis. Could be possible. This measurement method is described later in this specification. As a variant, if the synthesis step is carried out only in an alkaline sodium medium, the zeolite adsorbent material may already be in a sodium-exchanged form without any artificial intervention after the synthesis step.

  The Si / Al atomic ratio of the zeolite adsorbent material is measured by X-ray fluorescence elemental chemical analysis, a technique well known to those skilled in the art and described later herein. If necessary, a sodium exchange is performed according to the procedure detailed above before analysis.

  The term "Vmicro" is intended to mean the micropore volume of a zeolite adsorbent material, and the method for measuring Vmicro is described below. The term "Vmeso" is intended to mean the mesopore volume of the zeolite adsorbent material, and the method of measuring Vmeso is described below.

  According to a preferred embodiment, said at least one zeolite adsorbent material which can be used in connection with the present invention has a boundary value between -0.5 and 1.0, preferably without a boundary value. Between -0.1 and 0.9 without including, preferably between 0 and 0.9 without including the boundary value, more preferably between 0.2 and 0.8 without including the boundary value, It preferably has a ratio (Vmicro-Vmeso) / Vmicro between 0.4 and 0.8 without boundary values, preferably between 0.6 and 0.8 without boundary values, wherein Vmicro is , Micropore volume as measured by the Dubinin-Raduskevich method, and Vmeso is the mesopore volume as measured by the Barrett-Joyner-Halenda (BJH) method, There have been implemented as the subject an adsorbent material that has been changed at least 95% by sodium.

According to yet another embodiment, the at least one zeolite adsorbent material is expressed as cm ³ per gram of adsorbent material when measured on an adsorbent material that has been at least 95% exchanged with sodium. , 0.210 cm ³ . 0.360cm ³ from g ^-1. g ⁻¹ , preferably 0.230 cm ³ . 0.350cm ³ from g ^-1. g ⁻¹ , preferably 0.240 cm ³ . 0.350cm ³ from g ^-1. g ⁻¹ , more preferably 0.250 cm ³ . 0.350cm ³ from g ^-1. It has a micropore volume (Vmicro or Dubinin-Raduskevich volume) of between g- ¹ .

  It is also possible to calculate the overall Dubinin-Raduskevich volume of a FAU-type zeolite weighted by PNZ based on the Dubinin-Raduskevich micropore volume measured on the sodium-exchanged zeolite adsorbent material. It is.

The total macropore and mesopore volume of the zeolite adsorbent material which can be used in connection with the present invention, measured by mercury intrusion, is preferably 0.15 cm ³ . 0.5cm ³ from g ^-1. between g ^-1, preferably 0.20 cm ^3. 0.40cm ³ from g ^-1. between g ^-1, very preferably 0.20 cm ^3. 0.35cm ³ from g ^-1. g- ¹ and the measurements are performed on sorbent materials that have been exchanged for at least 95% by sodium.

  The volume fraction of macropores of the zeolite adsorbent material that can be used in connection with the present invention is preferably from 0.2 to 1 with respect to the total volume of macropores and mesopores, including boundary values. 0.0, very preferably between 0.4 and 0.8, even more preferably between 0.45 and 0.65, wherein the measurement is at least 95% exchanged by sodium for the zeolite adsorbent material Has been implemented for

  Zeolite adsorbent materials that can be used in connection with the present invention are known or can be prepared using known procedures, or are novel, and in this regard, these Zeolite adsorbent materials are an integral part of the present invention.

  According to yet another preferred embodiment, the use according to the invention uses a zeolite adsorbent material comprising at least one mesoporous FAU type zeolite. The term “mesoporous” refers to nanometer-sized nanopores having the microporosity inherent in the structure of the zeolite, but which can be easily distinguished by observation using a transmission electron microscope (TEM) as described, for example, in US Pat. It is intended to mean a zeolite that also has an internal cavity (mesoporous).

More specifically, the FAU-type zeolite of the zeolite adsorbent material is a mesoporous FAU-type zeolite, that is, 40 m ² , including boundary values, defined by the t-plot method described below. 400m ² from g ^-1. g ⁻¹ , preferably 60 m ² . 200m ² from g ^-1. Zeolite having an external surface area between g- ¹ . Thus, for the purposes of the present invention, "non-mesoporous zeolites" are strictly 40 m ² . A zeolite optionally having an external surface area of less than g- ¹ .

In particular, the zeolite adsorbent material that can be used in connection with the present invention comprises at least one FAU-type zeolite, wherein said at least one FAU-type zeolite is an inequality of 1 ≦ Si / Al <1.5, preferably Has an Si / Al ratio corresponding to the inequality 1 ≦ Si / Al ≦ 1.4, more preferably a Si / Al atomic ratio equal to 1.00 ± 0.05, wherein said Si / Al ratio is known to those skilled in the art. according to well-known ^techniques, and is measured by a solid state silicon 29 nuclear magnetic resonance (29 Si NMR).

  The Si / Al ratio of each zeolite present in the adsorbent has also been determined by NMR on solids.

  According to one preferred embodiment, the FAU-type zeolite of the zeolite adsorbent material is measured using a scanning electron microscope (SEM) and has a boundary value of less than 20 μm, preferably between 0.1 μm and 20 μm. , Preferably having a number average diameter between 0.1 μm and 10 μm, preferably between 0.5 μm and 10 μm, more preferably between 0.5 μm and 5 μm.

  According to yet another preferred embodiment, the zeolite adsorbent material comprises ions of group IA, IIA, IIIA, IB, IIB and IIIB of the periodic table, trivalent ions of the lanthanide or rare earth series, At least one cation selected from zinc (II) ion, silver (I) ion, copper (II) ion, chromium (III) ion, iron (III) ion, ammonium ion and / or hydronium ion; Preferred ions are calcium, lithium, sodium, potassium, barium, cesium, strontium, zinc and rare earth ions, more preferably sodium, calcium and lithium ions.

According to one embodiment, the zeolite adsorbent material that can be used in connection with the present invention is at least one selected from sodium, calcium, lithium and mixtures of two or three of these in any ratio. Wherein the content of at least one alkali metal or alkaline earth metal is preferably expressed as being in the form of an oxide,
The CaO content is between 0% and 20.5% by weight relative to the total weight of the zeolite adsorbent material, including the threshold value, preferably between 3% and 20% relative to the total weight of the zeolite adsorbent material; 0.5% by weight, preferably between 7.5% and 20.5% by weight relative to the total weight of the zeolite adsorbent material, preferably between 9% and 20% by weight relative to the total weight of the zeolite adsorbent material. Between 0.5% by weight;
The Li ₂ O content is between 0% and 12% by weight relative to the total weight of the zeolite adsorbent material, including the boundary values, preferably between 3% and 12% relative to the total weight of the zeolite adsorbent material; % By weight, preferably between 5% and 12% by weight relative to the total weight of the zeolite adsorbent material, preferably between 6.5% and 12% by weight relative to the total weight of the zeolite adsorbent material. And
The Na ₂ O content is between 0% and 22% by weight relative to the total weight of the zeolite adsorbent material, including the boundary values, preferably between 0% and 19% by weight relative to the total weight of the zeolite adsorbent material; % By weight, preferably between 0% and 15% by weight relative to the total weight of the zeolite adsorbent material, preferably between 0% and 10% by weight relative to the total weight of the zeolite adsorbent material. Preferably between 0% and 7% by weight relative to the total weight of the zeolite adsorbent material, advantageously between 0% and 2% by weight relative to the total weight of the zeolite adsorbent material;
It is understood that the zeolite adsorbent material comprises at least one of three metals selected from lithium, sodium and calcium;
The zeolite adsorbent material is optionally at least one of a content selected from lanthanides and actinides, preferably selected from lanthanides, generally between 0% and 10%, preferably between 0% and 7%. Further containing rare earth species,
-In some cases, the zeolite adsorbent material is other than lithium, sodium and calcium, and is preferably selected from, for example, transition metals such as potassium, barium, strontium, cesium and silver. The content is such that it further comprises one or more cations (less than 5%, preferably less than 2%, when expressed as%).

  According to the invention, the zeolite adsorbent material is used in a method for gas-phase separation, in particular pressure and / or temperature swing methods of PSA type or VSA type or VPSA type or RPSA type or TSA type and / or PTSA type. Is most particularly useful, appropriate and effective.

  More specifically, the present invention relates to the use of at least one zeolite adsorbent material comprising at least one FAU type zeolite as defined above for gas separation. The term "gas separation" is intended to mean the purification, pre-purification, removal and other separation of one or more gaseous compounds present in a mixture of one or more gaseous compounds.

  According to a preferred embodiment of the present invention, the zeolite adsorbent material that can be used for gas purification is a material that produces a slight pressure drop or only a pressure drop that is tolerable in the above uses.

  Thus, agglomerated and shaped zeolite adsorbent materials prepared by any technique known to those skilled in the art, such as extrusion, compression, agglomeration and atomization with a granulating plate or drum, are preferred. The proportions of cohesive binder and zeolite used are generally those of the prior art, i.e. 5 to 30 parts by weight binder per 95 to 70 parts by weight zeolite.

  The zeolite adsorbent material that may be used in connection with the present invention, whether in the form of a ball or extruded piece, is generally less than or equal to 7 mm, preferably between 0.05 mm and 7 mm, more preferably between 0.2 mm and It has a volume average diameter or average length between 5 mm, more preferably between 0.2 mm and 2.5 mm (the largest dimension if the zeolite adsorbent material is not spherical).

Zeolite adsorbent materials useful in the context of the present invention further have mechanical properties that are most particularly suitable for the application for which the zeolite adsorbent material is intended, i.e.,
-Measured according to standard ASTM 7084-04 for materials having a volume average diameter (D50) or length (maximum dimension if the zeolite adsorbent material is not spherical) of less than 1 mm, including a boundary value of 0. Bulk crush strength (BCS) in the layer state, between 5 MPa and 3 MPa, preferably between 0.75 MPa and 2.5 MPa
-Or measured according to the standards ASTM D4179 (2011) and ASTM D6175 (2013) for materials having a volume average diameter (D50) or length (the largest dimension if the zeolite adsorbent material is not spherical) of 1 mm or more. Thus, it further has a crushing strength in a single pellet state between 0.5 daN and 30 daN, including the boundary value, preferably between 1 daN and 20 daN.

According to another preferred embodiment, the use according to the invention has a high adsorptive capacity per unit volume, ie cm ³ .3 for adsorbent materials which have been exchanged by sodium for at least 95%. cm ⁻³ , expressed as 0.10 cm ³ . cm ^-3 , preferably 0.12 cm ³ . cm ⁻³ , more preferably 0.15 cm ³ . cm ⁻³ , more preferably 0.16 cm ³ . cm ^-3 , more preferably 0.18 cm ³ . cm ^-3 , preferably 0.20 cm ³ . At least one zeolite adsorbent material having a micropore volume per unit volume of greater than cm ^-3 is used.

  According to yet another embodiment, the use according to the invention is characterized by a strength of between 0 and 5% by weight, preferably between 0 and 3% by weight, measured at 950 ° C. according to the standard NF EN 196-2. It is preferred to use at least one zeolite adsorbent material having a heat loss.

  In particular, the invention relates to a method for purifying natural gas, in particular according to the pressure swing or temperature swing adsorption method or the pressure and temperature swing adsorption method (PSA or TSA or PTSA), preferably according to the TSA or PTSA method. It relates to the use of at least one zeolite adsorbent material as defined above for removing impurities present therein, preferably for removing carbon dioxide and / or mercaptans present in natural gas. For these types of applications, it is particularly preferred to use adsorbent materials, including FAU-type zeolites of the type selected from NaX and CaX and mixtures thereof, which are preferably mesoporous.

  For these types of applications, the volume average diameter (or longest length) is between 0.3 mm and 7.0 mm, including boundary values, preferably between 0.8 mm and 5.0 mm, Zeolite adsorbent materials, preferably between 2.0 mm and 5.0 mm, are preferred.

  According to another embodiment, the invention relates to a method for the non-cryogenic separation of industrial gases from gases in air, in particular for nitrogen adsorption when separating gases from air, in particular oxygen in air. For the enrichment of at least one zeolite adsorbent material as defined above. This use is particularly useful in pressure swing adsorption (PSA) devices with very short cycles (typically between 0.1 and 10 seconds, preferably between 0.1 and 5 seconds), in particular, for example, in patent application WO2008 / 152319, which is most particularly suitable for oxygen concentrators for respiratory assistance.

  In the case of the use according to the invention for the non-cryogenic separation of industrial gases from gases in the air, these methods are described in the prior art, in particular in the gas separation / purification method with zeolite adsorbents. It is known from the document EP 0893157.

  In applications of non-cryogenic separation of industrial gases and gases in air, preferably in applications of nitrogen separation for oxygen enrichment, preferably mesoporous NaX, LiX, CaX, LiCaX, NaLSX , LiLSX, CaLSX, LiCaLSX, and a zeolite adsorbent material containing at least one type of FAU-type zeolite selected from a mixture of two or more thereof, and the zeolite adsorbent material is in an oxide state. At least one alkali metal or alkaline earth selected from sodium, calcium, lithium and mixtures of two or three of these in any proportion, wherein the content is expressed as defined above. Including similar metals.

  More particularly, the use is most particularly suitable for nitrogen separation for oxygen enrichment, and most particularly for use in oxygen concentrators for respiratory assistance. In these cases, it is preferred to use at least one zeolite adsorbent material, including sodium, calcium and / or lithium, alone or as a mixture, and for these types of applications, it is mesoporous. NaX, LiX, CaX, LiCaX, NaLSX, LiLSX, CaLSX and LiCaLSX and a mixture of two or more thereof, preferably at least one of a kind selected from CaLSX, LiLSX and LiCaLSX. It is preferred to use a zeolite adsorbent material comprising a FAU type zeolite, more preferably at least one LiLSX type zeolite, preferably a mesoporous LiLSX type zeolite.

  In applications for the separation of industrial gases and gases in air, generally the average volume diameter is between 0.05 mm and 5 mm, preferably between 0.05 mm and 3.0 mm, more preferably between 0.05 mm and 2 mm. Zeolite adsorbent materials in the form of balls, which are between 0.0 mm, are preferred.

  For certain applications relating to oxygen enrichment of air, for example for oxygen concentrators for respiratory assistance, the average volume diameter is between 0.05 mm and 1 mm, preferably between 0.1 mm and 0.7 mm, Zeolite adsorbent materials in the form of balls, preferably between 0.3 mm and 0.6 mm, are preferred.

  According to another embodiment, the invention relates to the use of at least one zeolite adsorbent material as defined above for the purification of synthesis gas. One example of a method for purifying synthesis gas is described in patent EP 1312406. The synthesis gas covered here is in particular a synthesis gas based on hydrogen and carbon monoxide and / or hydrogen and nitrogen, more particularly a mixture of hydrogen and carbon monoxide and / or a mixture of hydrogen and nitrogen. A mixture-based synthesis gas comprising carbon dioxide and one or more other impurities that may be present, such as, but not limited to, nitrogen, carbon monoxide, oxygen, ammonia, hydrocarbons. And optionally one or more impurities selected from oxygen-containing derivatives, in particular alkanes, especially methane and alcohols, especially methanol, etc., or optionally depending on carbon dioxide and one or more of these impurities. Contaminated.

  The use according to the invention is therefore most particularly suitable for the production of hydrogen, preferably by pressure swing adsorption (PSA), for removing nitrogen, carbon monoxide, carbon dioxide, methane and other impurities. I have. For these types of applications, a type selected from NaX, LiX, LiLSX, CaX, CaLSX, LiCaX and LiCaLSX, which are preferably mesoporous and mixtures of two or more of these, preferably NaX Adsorbent materials are preferred, including FAU-type zeolites of the type selected from NaLSX and LiCaLSX.

  For these types of applications, the volume average diameter (or longest length) is between 0.3 mm and 7 mm, including the boundary value, preferably between 0.8 mm and 5.0 mm, more preferably Zeolite adsorbent materials that are between 1.0 mm and 3.0 mm are preferred.

  According to yet another embodiment, the present invention relates to a method for purifying the air of an air separation unit (ASU), especially hydrocarbons, carbon dioxide and nitrogen oxides, upstream of a cryogenic distillation unit. It also relates to the use of at least one zeolite adsorbent material as defined above for removing zeolites. These types of applications are preferably achieved by the PSA, TSA or PTSA methods, preferably by the TSA or PTSA methods, NaX, NaLSX, CaX and CaLSX, which are preferably mesoporous and of these Zeolite adsorbent materials are preferred, including FAU-type zeolites of the type selected from mixtures of two or more.

  For these types of applications, the volume average diameter (or longest length) should be between 0.3 mm and 7.0 mm, including boundary values, more preferably between 0.5 mm and 5.0 mm. Certain zeolite adsorbent materials are preferred.

According to another aspect, the present invention relates to a zeolite adsorbent material,
1 ≦ Si / Al <2.5, preferably 1 ≦ Si / Al ≦ 2, more preferably 1 ≦ Si / Al ≦ 1.8, more preferably 1 ≦ Si / Al ≦ 1.6 The Si / Al ratio of the adsorbent;
・ 0.08 cm ³ including the boundary value. 0.25cm ³ from g ^-1. g ⁻¹ , preferably 0.08 cm ³ . g ⁻¹ to 0.22 cm ³ . between g ^-1, more preferably 0.09 cm ^3. 0.20cm ³ from g ^-1. g ⁻¹ , more preferably 0.10 cm ³ . 0.20cm ³ from g ^-1. a mesopore volume between g- ¹ ;
-When Vmicro is measured by the Dubinin-Raduskevich method and Vmeso is measured by the BJH method, between -0.5 to 1.0 without including the boundary value, preferably without including the boundary value. -Between 0.1 and 0.9, preferably between 0 and 0.9 without boundary values, more preferably between 0.2 and 0.8 without boundary values, more preferably boundary A (Vmicro-Vmeso) / Vmicro ratio between 0.4 and 0.8 without values, preferably between 0.6 and 0.8 without boundaries;
0 <PNZ ≦ 30%, preferably 3% ≦ PNZ ≦ 25%, more preferably 3% ≦ PNZ ≦ 20%, advantageously 5% ≦ by weight relative to the total weight of the zeolite adsorbent material as measured by XRD A non-zeolitic phase (PNZ) content such that PNZ ≦ 20%, even more preferably 7% ≦ PNZ ≦ 18%, wherein all measurements are performed on a zeolite adsorbent material that has been exchanged for at least 95% by sodium. It relates to a zeolite adsorbent material, which is being implemented as a subject.

  The zeolite adsorbent material of the present invention as defined above is a novel material in that it results from agglomeration of at least one mesoporous FAU-type zeolite with a binder as described below, and has been previously defined. The term "mesoporous" refers to a nanometer that has the microporosity inherent in the structure of the zeolite, but is readily identifiable by observation using a transmission electron microscope (TEM) as described, for example, in US Pat. Represents a zeolite that also has internal cavities of size (mesoporous).

More specifically, the zeolite adsorbent material comprises at least one mesoporous FAU-type zeolite, i.e., 40 m ² .1 including boundary values, defined by the t-plot method described below. 400m ² from g ^-1. g ⁻¹ , preferably 60 m ² . 200m ² from g ^-1. zeolite having an external surface area between g- ¹ .

  Furthermore, the zeolitic adsorbent material according to the invention comprises at least one metal selected from lithium, sodium and calcium and mixtures of two or more of these metals, preferably selected from lithium, sodium and calcium. And preferably sodium and lithium or sodium and calcium or sodium, lithium and calcium. Zeolite adsorbent materials are also preferred, wherein the content of barium oxide is less than 0.5% by weight, preferably less than 0.3% by weight, more preferably less than 0.1% by weight, based on the total weight of the zeolite adsorbent material. .

  Due to these features, the zeolite adsorbent material according to the invention is particularly suitable for gas treatment, as described herein above.

  The zeolite adsorbent material according to the invention can be in all forms known to the person skilled in the art, and is preferably in simple geometric form, i.e. granular form, e.g. ball or rod type, i.e. spherical or cylindrical, respectively. It can be in granular form. Such simple forms are most particularly suitable because they are easy to process, especially because of their shape and size that are compatible with existing technology. In addition, these simple forms mean that the zeolite adsorbent material generates little pressure drop and has improved transfer properties, so that less energy is consumed by the method employed.

The zeolite adsorbent material according to the invention can be prepared according to any method known to the person skilled in the art, but is preferably specified, for example, W.I. At least one organic binder using a method for preparing mesoporous FAU as described by Schwieger (Angew. Chem. Int. Ed., (2012), 51 , 1962-1965). Or an inorganic binder, preferably an inorganic binder, more preferably a binder selected from zeolitic or non-zeolitable clays, especially kaolin, kaolinite, nacrites, dickite, halloysite, attapulgite, sepiolite, montmorillonite, bentonite, It can be prepared by agglomerating the crystals obtained with a binder selected from illite and metakaolin and a mixture of two or more of these clays in any proportion.

  Agglomeration and shaping can be carried out by all techniques known to those skilled in the art, such as extrusion, compression, agglomeration and atomization with a granulating plate or drum. These various techniques have the advantage of allowing the preparation of the sorbent material according to the invention, having the size and shape described above, which is most particularly suitable for gas treatment.

  The ratio of flocculant binder (eg clay shown above) and zeolite used for the above preparation are generally prior art ratios, but the desired PNZ content and the zeoliticity of the binder It changes according to the degree. These ratios can be readily calculated by those skilled in the art of synthesizing zeolite aggregates.

  Aggregates of zeolite adsorbent material, whether in the form of balls or extruded pieces, etc., are generally less than or equal to 7 mm, preferably between 0.05 mm and 7 mm, more preferably between 0.2 mm and 5 mm, more preferably Has a volume average diameter or average length between 0.2 mm and 2.5 mm (the largest dimension if the zeolite adsorbent material is not spherical).

  As already indicated, the process for producing the zeolite adsorbent material according to the invention can be easily reworked from the preparation methods known to the person skilled in the art, and the use of at least one mesoporous FAU type zeolite is Without substantial modification of the preparation methods known to those skilled in the art, which means that the preparation method is easy to carry out, fast, economical and therefore can be easily industrialized with a minimum of steps. means.

  The zeolite adsorbent material of the present invention preferably contains macropores, mesopores and micropores simultaneously. The term "macropore" is intended to mean a pore whose openings are greater than 50 nm, preferably between 50 nm and 400 nm. The term "mesopore" is intended to mean a pore in which the opening is between 2 nm and 50 nm, inclusive. The term "micropore" is intended to mean a pore having an opening of less than 2 nm.

According to one preferred embodiment, the zeolite adsorbent material according to the present invention, expressed as cm ³ per zeolitic adsorbent material 1g, 0.210cm ^3. 0.360cm ³ from g ^-1. g ⁻¹ , preferably 0.230 cm ³ . 0.350cm ³ from g ^-1. g ⁻¹ , more preferably 0.240 cm ³ . 0.350cm ³ from g ^-1. g ⁻¹ , preferably 0.250 cm ³ . 0.350cm ³ from g ^-1. It has a micropore volume (Dubinin-Raduskevich volume) of between g ^-1 , said micropore volume being measured for a zeolite adsorbent material which has been exchanged by sodium for at least 95%.

The total volume of macropores and mesopores of the zeolite adsorbent material according to the invention, measured by mercury intrusion, is preferably 0.15 cm ³ . 0.5cm ³ from g ^-1. between g ^-1, preferably 0.20 cm ^3. 0.40cm ³ from g ^-1. between g ^-1, very preferably 0.20 cm ^3. 0.35cm ³ from g ^-1. g- ¹ and the measurements are performed on sorbent materials that have been exchanged for at least 95% by sodium.

  The volume fraction of macropores of the zeolite adsorbent material is preferably between 0.2 and 1.0, including the boundary value, with respect to the total volume of macropores and mesopores, very preferably The measurement is performed on a zeolite sorbent material that is between 0.4 and 0.8, even more preferably between 0.45 and 0.65, with at least 95% exchanged by sodium.

  The size of the FAU-type zeolite crystals used to produce the zeolite adsorbent material of the present invention, and the size of the FAU-type zeolite elements in the zeolite adsorbent material are determined by observation using a scanning electron microscope (SEM). Measured. Preferably, the average diameter of the FAU type zeolite crystals is between 0.1 μm and 20 μm, preferably between 0.5 μm and 20 μm, more preferably between 0.5 μm and 10 μm. Observation by SEM can also confirm the presence of a non-zeolitic phase, including, for example, residual binder in the agglomerates (not converted during the optional zeolitizing step) or any other amorphous phase. To

According to one preferred embodiment, the zeolite adsorbent material according to the present invention, as measured by nitrogen adsorption, expressed as m ² per adsorbent 1 g 20 m ^2. g ⁻¹ , preferably 20 m ² . 300m ² from g ^-1. g ⁻¹ , more preferably 30 m ² . 250m ² from g ^-1. between g ^-1, more preferably ^{40 m} 2. 200m ² from g ^-1. between g ^-1, and most preferably ^{50 m} 2. 200m ² from g ^-1. Measurements have been performed on zeolite sorbent materials having an external surface area of between g ^-1 and at least 95% exchanged by sodium.

According to one preferred embodiment, the zeolite adsorbent material according to the invention has a high adsorption capacity per unit volume, i.e. cm ³ .0 for a zeolite adsorbent material which has been replaced by at least 95% by sodium. cm ⁻³ , expressed as 0.10 cm ³ . cm ^-3 , preferably 0.12 cm ³ . cm ⁻³ , more preferably 0.15 cm ³ . cm ⁻³ , more preferably 0.16 cm ³ . cm ^-3 , more preferably 0.18 cm ³ . cm ^-3 , preferably 0.20 cm ³ . It has a micropore volume per unit volume of more than cm ^-3 .

  According to one preferred embodiment, the zeolite adsorbent material according to the invention comprises at least one mesoporous FAU-type zeolite as defined above, wherein said at least one zeolite is 1 ≦ Si / Al <1. 5, preferably having a Si / Al ratio such that 1 ≦ Si / Al ≦ 1.4.

  According to a most particularly preferred embodiment, the at least one mesoporous FAU-type zeolite has a Si / Al ratio equal to 1.00 ± 0.05, wherein the measurement of the Si / Al ratio is at least 95% with sodium. It has been implemented for% exchanged zeolite adsorbent materials.

  According to yet another preferred embodiment, as indicated above, the zeolite adsorbent material comprises ions of groups IA, IIA, IIIA, IB, IIB and IIIB of the periodic table, a lanthanide series. Or selected from rare earth trivalent ions, zinc (II) ions, silver (I) ions, copper (II) ions, chromium (III) ions, iron (III) ions, ammonium ions and / or hydronium ions. Preferred ions include at least one cation, and preferred ions are calcium, lithium, sodium, potassium, barium, cesium, strontium, zinc and rare earth ions, more preferably sodium, calcium and It is lithium ion.

The metal content of the zeolite adsorbent material according to the invention, when expressed as being in the oxide state, is preferably the metal content indicated above, and more particularly:
The CaO content is between 0% and 20.5% by weight relative to the total weight of the zeolite adsorbent material, including the threshold value, preferably between 3% and 20% relative to the total weight of the zeolite adsorbent material; 0.5% by weight, preferably between 7.5% and 20.5% by weight relative to the total weight of the zeolite adsorbent material, preferably between 9% and 20% by weight relative to the total weight of the zeolite adsorbent material. Between 0.5% by weight;
The Li ₂ O content is between 0% and 12% by weight relative to the total weight of the zeolite adsorbent material, including the boundary values, preferably between 3% and 12% relative to the total weight of the zeolite adsorbent material; % By weight, preferably between 5% and 12% by weight relative to the total weight of the zeolite adsorbent material, preferably between 6.5% and 12% by weight relative to the total weight of the adsorbent material. Yes,
The Na ₂ O content is between 0% and 22% by weight relative to the total weight of the zeolite adsorbent material, including the boundary values, preferably between 0% and 19% by weight relative to the total weight of the zeolite adsorbent material; % By weight, preferably between 0% and 15% by weight relative to the total weight of the zeolite adsorbent material, preferably between 0% and 10% by weight relative to the total weight of the zeolite adsorbent material. Preferably between 0% and 7% by weight relative to the total weight of the zeolite adsorbent material, advantageously between 0% and 2% by weight relative to the total weight of the zeolite adsorbent material;
It is understood that the zeolite adsorbent material comprises at least one of three metals selected from lithium, sodium and calcium;
The zeolite adsorbent material is optionally at least one of a content selected from lanthanides and actinides, preferably selected from lanthanides, generally between 0% and 10%, preferably between 0% and 7%. Further containing rare earth species,
-In some cases, the zeolite adsorbent material is other than lithium, sodium and calcium, and is preferably selected from, for example, transition metals such as potassium, barium, strontium, cesium and silver. When expressed as a percentage, it is intended to further include one or more cations (less than 5%, preferably less than 2%).

  As indicated above, the content of barium oxide is less than 0.5% by weight, preferably less than 0.3% by weight, more preferably less than 0.1% by weight, based on the total weight of the zeolite adsorbent material. Certain zeolite adsorbent materials are also preferred.

  According to a further preferred embodiment, the zeolite adsorbent material according to the invention has no zeolite structure other than a FAU type (faujasite type) structure. The expression "having no zeolite structure other than the FAU type structure" refers to an XRD (X-ray diffraction) analysis of the adsorbent material according to the present invention, which shows that the faujasite type exceeds 5% by weight based on the total weight of the adsorbent material It is intended to mean that no zeolite structure other than the structure can be detected, preferably no more than 2% by weight of the zeolite structure other than the faujasite type structure.

According to yet another preferred embodiment, the present invention provides a method as described herein, wherein the 0.15 cm ³ . 0.5cm ³ from g ^-1. The total volume of the macropores and the mesopores between g ⁻¹ and the total volume of the macropores and the mesopores is preferably between 0.2 and 1 times including the boundary value, including the boundary value. Is a zeolite adsorbent material as defined above having a macroporous volume fraction of between 0.4 and 0.8 times, wherein the measurement is directed to an adsorbent material that has been replaced by at least 95% with sodium. It relates to a zeolite adsorbent material that is being implemented.

Characterization Methods The physical properties of the zeolite adsorbent materials have been evaluated by methods known to those skilled in the art, the main ones of these known methods being reproduced below.

Estimation of the number average diameter of the FAU type zeolite crystal contained in the zeolite adsorbent material used for preparing the zeolite adsorbent material is performed by observation with a scanning electron microscope (SEM). You.

  In order to estimate the size of the zeolite crystals in the sample, a set of images is taken at least at a magnification of 5000. The diameter of at least 200 crystals is then measured using dedicated software, for example, the Small View software published by LoGraMi. Accuracy is around 3%.

Zeolite adsorbent particle size The volume average diameter (or "volume average diameter") of the zeolite adsorbent material of the method according to the invention is determined by imaging according to the standard ISO 13322-2: 2006, whereby the sample is placed in front of the camera objective. It is determined by analyzing the particle size distribution of a sample of the sorbent material using a conveyor belt that allows it to pass.

  Next, the volume average diameter is calculated from the particle size distribution by applying the standard ISO 9276-2: 2001. As used herein, when referring to zeolite adsorbent materials, the designation "volume average diameter" or "size" is used. This accuracy is approximately 0.01 mm, as regards the size range of the sorbent material that can be used in connection with the present invention.

Chemical analysis of zeolite adsorbent material Si / Al ratio and degree of exchange The elemental chemical analysis of the zeolite adsorbent material can be performed according to various analytical methods known to those skilled in the art. Among these techniques, there can be mentioned a chemical analysis method by X-ray fluorescence using a wavelength dispersive spectrometer (WDXRF), for example, Bruker's Tiger S8 mechanical device, as described in the standard NF EN ISO 12677: 2011. .

  X-ray fluorescence is a non-destructive spectroscopy that utilizes the photoluminescence of atoms in the X-ray region to determine the elemental composition of a sample. Excitation of an atom, typically using an X-ray beam or electron bombardment, generates a particular radiation after the atom returns to the ground state. Conventionally, a measurement uncertainty of less than 0.4% by weight is obtained after calibration of each oxide.

  Other analysis methods include, for example, atomic absorption spectrometry (AAS) and inductively coupled plasma atomic emission spectroscopy on a device of the type Perkin Elmer 4300DV, for example, as described in the specifications NF EN ISO 21587-3 or NF EN ISO 21079-3. (ICP-AES) method.

The X-ray fluorescence spectrum has the advantage that it hardly depends on the chemical combination of elements, and as a result, a precise measurement is realized quantitatively and qualitatively. Conventionally, after calibration of each of the oxides SiO ₂ and Al ₂ O ₃ and various oxides (eg, oxides derived from exchangeable cations, eg, sodium cations), less than 0.4% by weight measurements Uncertainty has been obtained. The ICP-AES method is particularly suitable for the determination of lithium content, which makes it possible to calculate the lithium oxide content.

  Thus, the elemental chemical analysis allows verification of both the Si / Al ratio of the zeolite used in the zeolite adsorbent material and the Si / Al ratio of the zeolite adsorbent material. In the description of the present invention, the measurement uncertainty for the Si / Al ratio is ± 5%. Measurement of the Si / Al ratio of the zeolite present in the adsorbent material can also be performed by solid silicon nuclear magnetic resonance (NMR) spectroscopy.

The quality of ion exchange is related to the number of moles of the cation of interest in the zeolite adsorbent material after exchange. More specifically, the degree of exchange by a given cation is estimated by evaluating the ratio of the number of moles of said cation to the number of moles of all exchangeable cations. The respective amount of each cation is evaluated by chemical analysis of the corresponding cation. For example, the degree of exchange by sodium ions evaluates the ratio of the total number of Na ⁺ cations to the total number of exchangeable cations (eg, Ca ²⁺ , K ⁺ , Li ⁺ , Ba ²⁺ , Cs ⁺ , Na ^+, etc.). The amount of each cation is evaluated by chemical analysis of the corresponding oxide (Na ₂ O, CaO, K ₂ O, BaO, Li ₂ O, Cs ₂ O, etc.). This calculation also takes into account any oxides that may be present in the residual binder of the zeolite adsorbent material. However, it is believed that the amount of such oxides is not critical when compared to oxides derived from cations at the exchangeable sites of the zeolite of the zeolite adsorbent material according to the present invention.

Macropore and mesopore volumes Macropore and mesopore volumes are measured by mercury intrusion porosimetry on samples that have been at least 95% exchanged with sodium. The distribution of the pore volume contained in the macropores and mesopores is analyzed using a Micromeritics Autopore® 9500 mercury porosimeter.

  The experimental method described in the operating manual of the apparatus with reference to the standard ASTM D4284-83 consists in placing a pre-weighed sample of the zeolite adsorbent material to be measured (having a known loss on ignition) into a porosimeter cell, After a preliminary degassing (at a discharge pressure of 30 μm Hg for at least 10 minutes), the cell is filled with mercury at a given pressure (0.0036 MPa) and then the mercury is slowly penetrated into the porous network of the sample. In order to increase the pressure, pressure is applied so as to gradually increase to 400 MPa.

Therefore, in this specification, cm ³ . The macropore volume and mesopore volume of the zeolite adsorbent material, expressed as g- ¹ , were measured by mercury intrusion and were corrected for the weight of the sample as an anhydrous equivalent, i.e., loss on ignition. It is related to the weight of the zeolite adsorbent material.

Mechanical Strength of the Zeolite Adsorbent Material The bulk crush strength of the zeolite adsorbent material according to the present invention in the state of a layer is characterized according to the standard ASTM 7084-04. Particle crush strength is measured according to the standards ASTM D4179 and D6175 by means of a "particle crush strength" device sold by Vinci Technologies.

Micropore Volume Measurement Micropore volume measurement is estimated by conventional methods such as Dubinin-Raduskevich volume measurement (liquid nitrogen adsorption at 77K or liquid argon adsorption at 87K).

Dubinin-Raduskevich volume is determined by gas (e.g., nitrogen or argon) adsorption isotherm measurements at the liquefaction temperature as a function of zeolite pore opening; in the case of FAU, nitrogen will be selected. Prior to adsorption, the zeolite adsorbent material is degassed under vacuum (P <6.7 × 10 ⁻⁴ Pa) between 300 ° C. and 450 ° C. for a time between 9 and 16 hours. The measurement of the adsorption isotherm is then performed by a Micromeritics Model ASAP 2020, employing at least 35 measurement points at a relative pressure where the P / P0 ratio is between 0.002 and 1. The pore volume is determined from the obtained isotherms according to Dubinin and Raduskevich by applying the standard ISO 15901-3 (2007). The micropore volume, evaluated according to the Dubinin and Raduskevich equation, is expressed as cm ³ of liquid adsorbate per gram of zeolite adsorbent material. The uncertainty of the measurement was ± 0.003 cm ³ . g- ¹ and the measurements have been performed on zeolite adsorbent materials that have been exchanged by sodium for at least 95%.

Measurement of micropore volume per unit volume The micropore volume per unit volume is calculated from the above defined micropore volume by multiplying the above defined micropore volume by the apparent density of the zeolite adsorbent material. Is done. The apparent density is measured as described in standard DIN 8948 / 7.6.

Ignition Loss of Zeolite Adsorbent Material Ignition loss is measured at 950 ° C. ± 25 ° C. under an oxidizing atmosphere at a temperature of 950 ° C. ± 25 ° C. as described in the standard NF EN196-2 (April 2006). Measured by calcination. The standard deviation of the measurement is less than 0.1%.

Qualitative and Quantitative Analysis by X-Ray Diffraction The purity of the zeolite in the zeolite adsorbent material is assessed by X-ray diffraction analysis known to those skilled in the art under the acronym XRD. The identification of the purity is performed by a Bruker XRD device.

  This analysis allows the identification of the various zeolites present in the sorbent material, in that each zeolite has a unique diffraction pattern defined by the arrangement of the diffraction peaks and the relative intensity of the diffraction peaks. There is.

  After grinding the zeolite adsorbent material, it is leveled on the sample holder by simple mechanical compression.

The conditions under which a diffraction pattern is acquired by a Bruker D5000 machine are as follows.
Cu tubes used at 40 kV and 30 mA,
・ Slit size (for divergence, for scattering and for analysis) = 0.6 mm,
・ Filter: Ni,
Rotation of the device containing the sample: 15 rpm,
Measurement range: 3 ° <2θ <50 °,
・ Increment: 0.02 °
-Counting time for each increment: 2 seconds.

  Interpretation of the resulting diffraction pattern is performed by EVA software, which identifies the zeolite using the 2011 release base of ICDD PDF-2.

  The amount of the FAU-type zeolite fraction by weight is determined by XRD analysis. The method is also used to determine the amount of non-FAU zeolite fraction. After this analysis has been performed with a Bruker brand machine, the amount of zeolite fraction by weight is evaluated using Bruker TOPAS software.

Measurement of external surface area (m ² / g) by “t-plot” method The “t-plot” calculation method makes it possible to calculate the micropore surface area by utilizing the adsorption isotherm data Q ads = f (P / P0). I do. From this micropore surface area, the external surface area can be estimated by determining the difference from the BET surface area calculated as the total pore surface area as m ² / g (S BET = micropore surface area + external surface area) .

In order to calculate the micropore surface area by the t-plot method, the curve Q ads (as a function of the thickness of the layer as a function of the partial pressure P / P0 to be formed in the non-porous reference material, t) cm ³ t function .g ^-1) plot the (log (P / P0): applied Harkins-Jura equation: [13.99 / (0.034-log (P / P0)) ^ 0.5 A line defining the adsorbed intercept point Q may be plotted, with an interval t between 0.35 nm and 0.5 nm, thus calculating the pore surface area. If the material is not microporous, a straight line passes through 0. The measurements are based on zeolite sorbent material that has been exchanged for at least 95% by sodium. It is implemented as an elephant.

Measurement of Mesopore Volume Measurement of mesopore volume on samples that have been exchanged for at least 95% by sodium is evaluated by conventional methods such as Barret-Joyner-Halenda volumetric measurement (adsorption of liquid nitrogen at 77K). Is done.

The mesopore volume is determined by gas (eg, nitrogen) adsorption isotherm at the liquefaction temperature as a function of zeolite pore opening, and in the case of FAU, nitrogen will be selected. Prior to adsorption, the zeolite adsorbent material is degassed under vacuum (P <6.7 × 10 ⁻⁴ Pa) between 300 ° C. and 450 ° C. for a time between 9 and 16 hours. The measurement of the adsorption isotherm is then performed by a Micromeritics Model ASAP 2020, employing at least 35 measurement points at a relative pressure where the P / P0 ratio is between 0.002 and 1. The mesopore volume is determined from the obtained isotherms according to Barret-Joyner-Halenda by application of the standard ISO 15901-2 (2007). Mesopore volume, evaluated according to the Barret-Joyner-Halenda equation, is expressed as cm ³ of liquid adsorbate per gram of zeolite adsorbent material.

  The following examples serve to illustrate the invention, but are not intended to limit the scope of the invention, which is defined by the appended claims.

[Example 1]
Preparation of zeolite adsorbent material according to the present invention
Step 1 : Si / Al ratio equal to 1.01 and 95 m ² . Synthesis of mesoporous LSX-type zeolite crystals with external surface area of g- ¹ a) Preparation of growth gel: reactor stirred at 250 rpm by Archimedes screw 3 liter volume equipped with heating jacket, temperature probe and stirrer in a stainless steel reactor, sodium hydroxide 300g (NaOH), 85% potassium hydroxide 264 g, containing _Al 2 _{O 3} alumina trihydrate 169 g (65.2 wt%, _Al 2 O ₃ - and _3H 2 O) and 25 ° C. aluminate solution containing water 1200g of sodium silicate 490 g, and a silicic acid solution containing NaOH and 25 ° C. water 470g of 29.4 g, 250 rpm A growth gel is prepared by mixing at a stirring speed of 5 minutes.

The stoichiometry of the growth gel is as follows. _{4.32Na 2 O / 1.85K 2 O /} Al 2 O 3 /2.0SiO 2 / 114H 2 O. Homogenization of the growth gel is performed at 250 rpm with stirring at 25 ° C. for 15 minutes.

b) was prepared in the same way as adding growth gel nucleation gel, 40 ° C. and aged 1 hour _{at, 12Na 2 O / Al 2 O} 3 / 10SiO 2 / 180H 2 O nucleation gel of the composition of 11.6 g (ie 0.4% by weight) are added to the growing gel at 25 ° C. with stirring at 300 rpm. After homogenization at 250 rpm for 5 minutes, reduce the stirring speed to 50 rpm and continue stirring for 30 minutes.

c) Introduction of the structuring agent into the reaction medium 35.7 g of a 60% solution of [3- (trimethoxysilyl) propyl] octadecyldimethylammonium chloride (TPOAC) in methanol (MeOH) are reacted for 5 minutes at a stirring speed of 250 rpm. It is introduced into the medium (TPOAC / Al ₂ O ₃ molar ratio = 0.04). Next, the aging step is performed at 30 ° C. for 20 hours at 50 rpm, and then crystallization is started.

d) Two-stage crystallization Maintaining the stirring speed at 50 rpm, then increasing the set point of the reactor jacket, the temperature of the reaction medium was raised to 60 ° C. over 5 hours, followed by a 21-hour steady temperature step at 60 ° C. Program to 63 ° C. in a linear fashion as described. The set point of the reactor jacket is then set at 102 ° C., such that the temperature of the reaction medium increases by 95 ° C. over 60 minutes. After 3 hours at a steady temperature stage of 95 ° C., the reaction medium is cooled by circulating cold water in the jacket and the crystallization is stopped.

e) Filtration / washing After the solids are collected by the sintered body, they are washed with deionized water to neutral pH.

f) Drying / calcination Perform drying in an oven at 90 ° C. for 8 hours to characterize the product.

The calcination of the dried product, required to eliminate both micropores (water) and mesopores by removal of the structurant, takes 9 hours under vacuum (P <6.7 × 10 ⁻⁴ Pa) This is done by degassing under vacuum, with a step-wise increase from 50 ° C. to 400 ° C. over a period of between 16 and 16 hours.

After degassing at 400 ° C. under vacuum for 10 hours, the micropore volume and the external surface area, measured according to the t-plot method from the nitrogen adsorption isotherm at 77 K, are each 0.215 cm ³ . g ^-1 and ^95m 2. g- ¹ . The number average diameter of the crystals is 6 μm. The mesopore diameter calculated from the nitrogen adsorption isotherm by the DFT method is between 5 nm and 10 nm. The XR diffraction pattern corresponds to a pure faujasite type (FAU type) structure, and no LTA type zeolite is detected. The Si / Al molar ratio of the mesoporous LSX measured by X-ray fluorescence is equal to 1.01.

  FIG. 1 shows an image obtained by transmission electron microscopy (TEM) of the zeolite synthesized as described above.

Step 2 : Preparation of Mesoporous LSX-Type Zeolite Aggregates In the description below, the weights given are expressed as anhydrous equivalents.

  1700 g of the mesoporous LSX zeolite crystal obtained in step 1, 300 g of Zeoclay® attapulgite sold by CECA, and an amount such that the loss on ignition of the paste before molding is 35%. Prepare a homogeneous mixture consisting of water. The paste thus prepared is used on a granulation plate to prepare balls made from agglomerated zeolite adsorbent material. The resulting balls are screened by sieving to collect balls having a diameter between 0.3 and 0.8 mm and a volume average diameter equal to 0.55 mm.

  Dry the balls at 80 ° C. overnight in a ventilated oven. The balls are then calcined at 550 ° C. for 2 hours under nitrogen flushing, and then calcined at 550 ° C. for 2 hours under flushing with decarbonated dry air.

Step 3 : Lithium exchange and activation of mesoporous LSX zeolite aggregates 20 ml. Five successive exchanges are performed with a 1 M solution of lithium chloride in the ratio g- ¹ . Each exchange lasts 4 hours at 100 ° C., performing an intermediate wash so that excess salt can be removed at each step. In the last step, 20 ml. Four washes are performed at ambient temperature to give a ratio of g- ¹ .

  Dry the balls at 80 ° C. overnight in a ventilated oven. The balls are then activated at 550 ° C. for 2 hours under nitrogen flushing.

The content of lithium oxide Li ₂ O measured by ICP-AES is a 8.9% by weight relative to the total weight of the zeolite adsorbent material. The volume average diameter of the ball is 0.55 mm. The bulk crush strength of the lithium-exchanged mesoporous LSX-type zeolite ball in the state of a layer is 2.6 daN.

Step 4 : Characterization To characterize the zeolite adsorbent material, the zeolite adsorbent material is exchanged by sodium for at least 95% by the following method. The zeolite adsorbent material was added to a sodium chloride solution containing 1 mole of NaCl per liter with a 10 ml. It is introduced at 90 ° C. for 3 hours at g ⁻¹ . This operation is repeated four times. Between each exchange, the solid was successively removed to remove 20 ml. Wash four times by immersion in water in the ratio g ⁻¹ and then dry in air at 80 ° C. for 12 hours before analyzing by X-ray fluorescence. The weight percentage of sodium oxide in the zeolite adsorbent material is equal to 18.2% and has a stability between exchange operation 3 and exchange operation 4 of less than 1%. Dry the balls at 80 ° C. overnight in a ventilated oven. The balls are then activated at 550 ° C. for 2 hours under nitrogen flushing.

The external surface area is 99 m ² . g ⁻¹ and the micropore volume is 0.264 cm ³ . g- ¹ . Micropore volume per unit volume is sodium Replaced zeolitic adsorbent material 1 cm ³ per 0.150cm ^3. The mesopore volume is 0.165 cm ³ . g ^-1 . The total volume of macropores and mesopores, measured by mercury intrusion, is 0.42 cm ³ . g- ¹ .

  The Si / Al atomic ratio of the adsorbent is 1.25. The Si / Al ratio of the zeolite present in the adsorbent zeolite material is equal to 1.01 and has been measured by solid silicon 29 NMR.

  The content of non-zeolite phase (PNZ), expressed by weight relative to the total weight of the sorbent, as determined by XRD, is 15.3%.

[Example 2]
Zeolite adsorbent material for comparison CECA's Silipore (R) Nitroxy (R) SXSDM sieve is a material based on LiLSX-type zeolite which is aggregated together with attapulgite. The average diameter per unit volume of the ball is equal to 0.55 mm. The content of lithium oxide Li ₂ O, determined by ICP-AES, is 9.2% by weight, based on the total weight of the sieve.

  As in Step 4 of Example 1, sodium exchange is performed to obtain a solid that has been exchanged by sodium for at least 95%. As mentioned above, this result is obtained by four consecutive exchanges.

  The weight percentage of sodium oxide of the zeolite adsorbent material obtained by X-ray fluorescence is equal to 18.4% and has a stability between exchange operation 3 and exchange operation 4 of less than 1%. Dry the balls at 80 ° C. overnight in a ventilated oven. The balls are then activated at 550 ° C. for 2 hours under nitrogen flushing.

The external surface area is 31 m ² . g ⁻¹ and the pore volume is 0.265 cm ³ . g- ¹ . Micropore volume per unit volume is sodium Replaced zeolitic adsorbent material 1 cm ³ per 0.172cm ^3. The mesopore volume is 0.07 cm ³ . g ^-1 . The total volume of macropores and mesopores measured by mercury intrusion is 0.31 cm ³ . g- ¹ .

  The Si / Al atomic ratio of the adsorbent is 1.23. The content of non-zeolite phase (PNZ), expressed by weight relative to the total weight of the sorbent, as determined by XRD, is 15.3%.

[Example 3]
N ₂ / O ₂ Separation Test in Fixed Bed of Adsorbent by Pressure Swing Adsorption N ₂ / O ₂ Separation Test It is carried out by adsorption in a single column according to the principles presented by Alpay et al. (Id.).

FIG. 2 describes the manufactured assembly. Dry air (3) is intermittently supplied by a valve (4) to a column (1) packed with a zeolite adsorbent material (2) and having an inner diameter of 27.5 mm and an internal height of 600 mm. The time during which the stream (3) is fed to the column (1) is called the adsorption time. When no dry air is supplied to the column (1), the stream (3) is discharged to the atmosphere by the valve (5). The zeolite adsorbent material preferentially absorbs nitrogen, so that oxygen-enriched air leaves the column via check valve (6) and enters the buffer tank (7). The regulating valve (8) is 1NL. Continue to deliver gas to outlet (9) at a constant flow rate fixed at min- ¹ .

  When column (1) is not receiving feed, i.e. when valve (4) is closed and valve (5) is open, column (1) is exposed to atmospheric air (11) for a period called the desorption time. The pressure is reduced by the valve (10) leading to the pressure. The adsorption step and the desorption step continue so as to be performed alternately. The duration of these stages is fixed from cycle to cycle, but can be adjusted. Table 1 shows the respective valve states according to the adsorption stage and the desorption stage.

  The tests are performed sequentially using the zeolite adsorbent material of Example 1 (according to the invention) and the zeolite adsorbent material of Example 2 (for comparison). The column is charged with a fixed volume of 204.5 g and 239.7 g of adsorbent material, respectively. The pressure at the inlet is fixed at 280 kPa.

The outlet flow rate is 1 NL. min ⁻¹ . The adsorption time is fixed at 0.25 seconds. The desorption time can be changed between 0.25 seconds and 1.25 seconds.

  The oxygen concentration at the outlet (9) is measured by a Servomex 570A oxygen analyzer.

  FIG. 3 shows the oxygen content of the stream produced at the outlet (9) as a function of the desorption time defined for the materials of Example 1 and Example 2. Despite the lower weight charged in the column, the material of Example 1 (according to the invention) (in comparison with the solid of Example 2) It has proven to be much more efficient (in terms of oxygen content).

Claims (24)

Use of at least one zeolite adsorbent material comprising at least one FAU type zeolite for gas separation, said adsorbent comprising:
- measured by nitrogen adsorption, expressed as ^{m 2} per adsorbent 1 g ^{20 m} 2. g ⁻¹ , preferably 20 m ² . 300m ² from g ^-1. g ⁻¹ , more preferably 30 m ² . 250m ² from g ^-1. g ⁻¹ , even more preferably 40 m ² . 200m ² from g ^-1. g- ¹ , most specifically 50 m ² . 200m ² from g ^-1. an external surface area between g- ¹ ;
0 <PNZ ≦ 30%, preferably 3% ≦ PNZ ≦ 25%, more preferably 3% ≦ PNZ ≦ 20%, advantageously 3% ≦ PNZ ≦ 30% by weight based on the total weight of the adsorbent as measured by XRD (X-ray diffraction) Is a non-zeolite phase (PNZ) content such that 5% ≦ PNZ ≦ 20%, even more preferably 7% ≦ PNZ ≦ 18%;
・ 0.08 cm ³ including the boundary value. 0.25cm ³ from g ^-1. g ⁻¹ , preferably 0.08 cm ³ . g ⁻¹ to 0.22 cm ³ . between g ^-1, more preferably 0.09 cm ^3. 0.20cm ³ from g ^-1. g ⁻¹ , more preferably 0.10 cm ³ . 0.20cm ³ from g ^-1. a mesopore volume between g- ¹ ;
The Si / Al of the adsorbent between 1 and 2.5, preferably between 1 and 2.0, more preferably between 1 and 1.8, and most preferably between 1 and 1.6 Use, wherein all the measurements are performed on the sorbent material that has been exchanged for at least 95% by sodium.   The at least one zeolite adsorbent material has a boundary value between -0.5 and 1.0, preferably without a boundary value between -0.1 and 0.9, preferably a boundary value Between 0 and 0.9 without the value, more preferably between 0.2 and 0.8 without the value of the boundary, more preferably between 0.4 and 0.8 without the value of the boundary Having a (Vmicro-Vmeso) / Vmicro ratio between 0.6 and 0.8, preferably excluding boundary values, where Vmicro is the micropore volume measured by the Dubinin-Raduskevich method, and Vmeso Is the mesopore volume as measured by the Barrett-Joyner-Halenda (BJH) method, with all the above measurements being at least 95% exchanged by sodium. It is implemented as an object zeolite adsorbent material, Use according to claim 1. Wherein the at least one zeolite adsorbent material, when measured with said zeolite adsorbent material exchanged at least 95% by sodium as the target, expressed as cm ³ per zeolitic adsorbent material 1g, 0.210cm ^3. 0.360cm ³ from g ^-1. g ⁻¹ , preferably 0.230 cm ³ . 0.350cm ³ from g ^-1. g ⁻¹ , preferably 0.240 cm ³ . 0.350cm ³ from g ^-1. g ⁻¹ , more preferably 0.250 cm ³ . 0.350cm ³ from g ^-1. 3. Use according to claim 1 or 2, having a micropore volume (Dubinin-Raduskevich volume) of between g- ¹ .   The at least one FAU-type zeolite has an Si / Al ratio corresponding to an inequality of 1 ≦ Si / Al <1.5, preferably an inequality of 1 ≦ Si / Al ≦ 1.4, more preferably 1.00 ± 4. Use according to any one of the preceding claims, having a Si / Al atomic ratio equal to 0.05, wherein the Si / Al ratio is measured by solid silicon 29 NMR.   The zeolitic adsorbent material comprises ions of groups IA, IIA, IIIA, IB, IIB and IIIB of the periodic table, lanthanide or rare earth trivalent ions, zinc (II) ions, silver (I) Ion, copper (II) ion, chromium (III) ion, iron (III) ion, ammonium ion and / or at least one cation selected from hydronium ion, and preferred ions are calcium ion, lithium ion, The sodium ion, potassium ion, barium ion, cesium ion, strontium ion, zinc ion and rare earth ion, more preferably sodium ion, calcium ion and lithium ion. use. Use of at least one zeolite in the adsorbent material according to any of the preceding claims, wherein the at least one material is sodium, calcium, lithium and any of these in any proportion. Containing at least one alkali metal or alkaline earth metal selected from a mixture of two or three of the following, wherein the content of at least one alkali metal or alkaline earth metal is expressed as being in an oxide state. When
The CaO content is between 0% and 20.5% by weight relative to the total weight of the zeolite adsorbent material, including the boundary values, preferably 3% by weight relative to the total weight of the zeolite adsorbent material; To 20.5% by weight, preferably 7.5% to 20.5% by weight based on the total weight of the zeolite adsorbent material, preferably 9% by weight based on the total weight of the zeolite adsorbent material. % To 20.5% by weight,
The Li ₂ O content is between 0% and 12% by weight relative to the total weight of the zeolite adsorbent material, including the boundary values, preferably 3% by weight relative to the total weight of the zeolite adsorbent material To 12% by weight, preferably between 5% and 12% by weight based on the total weight of the zeolite adsorbent material, preferably 6.5% to 12% by weight based on the total weight of the zeolite adsorbent material. Weight percent,
The Na ₂ O content is between 0% and 22% by weight relative to the total weight of the zeolite adsorbent material, including the boundary value, preferably 0% by weight relative to the total weight of the zeolite adsorbent material To 19% by weight, preferably 0% to 15% by weight relative to the total weight of the zeolite adsorbent material, preferably 0% to 10% by weight relative to the total weight of the zeolite adsorbent material. Preferably entirely between 0% and 7% by weight relative to the total weight of the zeolite adsorbent material, advantageously between 0% and 2% by weight relative to the total weight of the zeolite adsorbent material Between
It is understood that the zeolite adsorbent material comprises at least one of three metals selected from lithium, sodium and calcium;
The zeolite adsorbent material is optionally at least one of a content selected from lanthanides and actinides, preferably selected from lanthanides, generally between 0% and 10%, preferably between 0% and 7%; Further containing rare earth species,
-In some cases, the zeolite adsorbent material is other than lithium, sodium and calcium, and is preferably selected from transition metals such as potassium, barium, strontium, cesium and silver, in small amounts (in the form of oxides). Use of less than 5%, preferably less than 2%, when expressed as%).   7. A process according to claim 1, wherein the process comprises purifying natural gas, in particular removing impurities present in natural gas, preferably removing carbon dioxide and / or mercaptans present in natural gas. Use according to item 1.   The use according to claim 7, wherein the zeolite adsorbent material comprises at least one FAU-type zeolite of the type selected from NaX and CaX, which are preferably mesoporous, and mixtures thereof.   7. Use according to any one of the preceding claims for non-cryogenic separation of industrial gases from gases in air.   10. Use according to claim 9, for nitrogen adsorption when separating gas from air, in particular for the concentration of oxygen in air.   The zeolite adsorbent material is preferably at least one selected from the group consisting of NaX, LiX, CaX, LiCaX, NaLSX, LiLSX, CaLSX, and LiCaLSX, which are preferably mesoporous, and a mixture of two or more of these. 11. Use according to claim 9 or 10, comprising a FAU type zeolite.   12. Use according to any one of claims 9 to 11 in pressure swing adsorption devices with very short cycles, in particular in oxygen concentrators for respiratory assistance.   The zeolite adsorbent material is preferably at least one FAU-type zeolite of a type selected from CaLSX, LiLSX and LiCaLSX, which is preferably mesoporous, more preferably at least one type of LiLSX-type zeolite, preferably mesoporous. 13. Use according to claim 12, comprising a LiLSX type zeolite.   7. Use according to any one of the preceding claims for the purification of a synthesis gas optionally contaminated with carbon dioxide and one or more other impurities that may be present.   The zeolite adsorbent material is preferably selected from NaX, LiX, LiLSX, CaX, CaLSX, LiCaX and LiCaLSX, which are preferably mesoporous, and a mixture of two or more of these, preferably NaX, NaLSX and 15. Use according to claim 14, comprising at least one FAU-type zeolite of the type selected from LiCaLSX.   7. The method according to claim 1, for purifying air in an air separation unit (ASU), particularly for removing hydrocarbons, carbon dioxide and nitrogen oxides, upstream of the cryogenic distillation unit. 8. Use of the description.   The zeolite adsorbent material comprises at least one FAU zeolite of a type selected from NaX, NaLSX, CaX and CaLSX, which are preferably mesoporous, and mixtures of two or more thereof. Use according to item 16. A zeolite adsorbent material,
1 ≦ Si / Al <2.5, preferably 1 ≦ Si / Al ≦ 2, more preferably 1 ≦ Si / Al ≦ 1.8, more preferably 1 ≦ Si / Al ≦ 1.6 The Si / Al ratio of the adsorbent;
・ 0.08 cm ³ including the boundary value. 0.25cm ³ from g ^-1. g ⁻¹ , preferably 0.08 cm ³ . g ⁻¹ to 0.22 cm ³ . between g ^-1, more preferably 0.09 cm ^3. 0.20cm ³ from g ^-1. g ⁻¹ , more preferably 0.10 cm ³ . 0.20cm ³ from g ^-1. a mesopore volume between g- ¹ ;
-When Vmicro is measured by the Dubinin-Raduskevich method and Vmeso is measured by the BJH method, between -0.5 to 1.0 without including the boundary value, preferably without including the boundary value. -Between 0.1 and 0.9, preferably between 0 and 0.9 without boundary values, more preferably between 0.2 and 0.8 without boundary values, more preferably boundary A (Vmicro-Vmeso) / Vmicro ratio between 0.4 and 0.8 without values, preferably between 0.6 and 0.8 without boundaries;
0 <PNZ ≦ 30%, preferably 3% ≦ PNZ ≦ 25%, more preferably 3% ≦ PNZ ≦ 20%, advantageously 5% by weight relative to the total weight of the zeolite adsorbent material as measured by XRD ≦ PNZ ≦ 20%, even more preferably 7% ≦ PNZ ≦ 18%, such that the zeolite adsorption wherein all said measurements have been exchanged by sodium by at least 95% Zeolite adsorbent material, which is implemented for adsorbent materials. Expressed as cm ³ per zeolitic adsorbent material 1g, 0.210cm ^3. 0.360cm ³ from g ^-1. g ⁻¹ , preferably 0.230 cm ³ . 0.350cm ³ from g ^-1. g ⁻¹ , more preferably 0.240 cm ³ . 0.350cm ³ from g ^-1. g ⁻¹ , preferably 0.250 cm ³ . 0.350cm ³ from g ^-1. 19. Zeolite adsorption according to claim 18, having a micropore volume of between g- ¹ , wherein said micropore volume is measured for said zeolite adsorbent material which has been exchanged by sodium for at least 95%. Agent material. When the total volume of the macropores and mesopores measured by mercury intrusion was measured said zeolite adsorbent material exchanged at least 95% by sodium as the target, 0.15 cm ^3. 0.5cm ³ from g ^-1. between g ^-1, preferably 0.20 cm ^3. 0.40cm ³ from g ^-1. between g ^-1, very preferably 0.20 cm ^3. 0.35cm ³ from g ^-1. 20. Zeolite adsorbent material according to claim 18 or 19, which is between g- ¹ . 20 m ² when measured said zeolitic adsorbent material exchanged at least 95% as the target by sodium, as determined by nitrogen adsorption, expressed as m ² per adsorbent 1g. g ⁻¹ , preferably 20 m ² . 300m ² from g ^-1. g ⁻¹ , more preferably 30 m ² . 250m ² from g ^-1. between g ^-1, more preferably ^{40 m} 2. 200m ² from g ^-1. g ^-1 , most preferably 50 m ² . 200m ² from g ^-1. 21. The zeolitic sorbent material according to any one of claims 18 to 20, having an external surface area between g- ¹ . Cm ³ for zeolite adsorbent material at least 95% exchanged by sodium. cm ⁻³ , expressed as 0.10 cm ³ . cm ^-3 , preferably 0.12 cm ³ . cm ⁻³ , more preferably 0.15 cm ³ . cm ⁻³ , more preferably 0.16 cm ³ . cm ^-3 , more preferably 0.18 cm ³ . cm ^-3 , preferably 0.20 cm ³ . 22. The zeolitic adsorbent material according to any one of claims 18 to 21, having a micropore volume per unit volume of greater than cm- ³ . When the metal content is expressed as being in the oxide state,
The CaO content is between 0% and 20.5% by weight relative to the total weight of the zeolite adsorbent material, including the boundary values, preferably 3% by weight relative to the total weight of the zeolite adsorbent material; To 20.5% by weight, preferably 7.5% to 20.5% by weight based on the total weight of the zeolite adsorbent material, preferably 9% by weight based on the total weight of the zeolite adsorbent material. Between 2% and 20.5% by weight;
The Li ₂ O content is between 0% and 12% by weight relative to the total weight of the zeolite adsorbent material, including the boundary values, preferably 3% by weight relative to the total weight of the zeolite adsorbent material To 12% by weight, preferably between 5% and 12% by weight, preferably 6.5% to 12% by weight, based on the total weight of the zeolite adsorbent material. Between
The Na ₂ O content is between 0% and 22% by weight relative to the total weight of the zeolite adsorbent material, including the boundary value, preferably 0% by weight relative to the total weight of the zeolite adsorbent material To 19% by weight, preferably 0% to 15% by weight relative to the total weight of the zeolite adsorbent material, preferably 0% to 10% by weight relative to the total weight of the zeolite adsorbent material. Preferably entirely between 0% and 7% by weight relative to the total weight of the zeolite adsorbent material, advantageously between 0% and 2% by weight relative to the total weight of the zeolite adsorbent material Between
It is understood that the zeolite adsorbent material comprises at least one of three metals selected from lithium, sodium and calcium;
The zeolite adsorbent material is optionally at least one of a content selected from lanthanides and actinides, preferably selected from lanthanides, generally between 0% and 10%, preferably between 0% and 7%. Further containing rare earth species,
-In some cases, the zeolite adsorbent material is other than lithium, sodium and calcium, and is preferably selected from, for example, transition metals such as potassium, barium, strontium, cesium and silver. 23. Zeolite according to any one of claims 18 to 22, which further comprises one or more cations (when expressed as%, less than 5%, preferably less than 2%). Sorbent material. 0.15 cm ³ measured by mercury intrusion. 0.5cm ³ from g ^-1. The total volume of the macropores and the mesopores between g ⁻¹ and the total volume of the macropores and the mesopores is preferably between 0.2 and 1 times including the boundary value, including the boundary value. 24. The zeolitic sorbent material according to any one of claims 18 to 23, wherein the zeolite adsorbent material has a macropore volume fraction of between 0.4 and 0.8. A zeolite adsorbent material that has been implemented for% exchanged adsorbent material.

Images